New water-soluble mordant azophthalocyanine dyestuffs and process for making same



NEW WATER-SOLUBLE MORDAN T AZOPHTHALO- CYANINE DYESTUFFS AND PROCESS FOR MAKING SAME Willy Brentano, Arlesheim, near Basel, Switzerland, assignor to Durand & Huguenin A. G., Basel, Switzerland, a Swiss company No Drawing. Application January 12, 1954, Serial No. 403,654

Claims priority, application Switzerland January 14, 1953 7 Claims. (Cl. 260-146) In copending U. S. patent application, Serial No. 329,727, filed January 5, 1953 (since granted as U. S. Patent No. 2,706,199) there are described water-soluble esters of phthalocyanine tetrasulphonic acids, which contain at least one salicylic acid group and are blue to green dyestuffs which are suitable for dyeing and printing textiles. These dyestufis are distinguished by their mordant character and yield especially valuable blue tints, having very good properties of fastness.

There are also described in copending U. S. patent application, Serial No. 370,612, filed July 27, 1953, Water-soluble mordant azophthalocyanine dyestufis which are obtained by reacting a phthalocyanine sulphochloride derived from a phthalocyanine tetrasulphonic acid with 1-4 molecular proportions of at least one aminoazodyestuff which contains a salicylic acid grouping. These dyestuffs yield green to olive tints which in some cases possess very good properties of fastness.

The present invention provides new, very valuable, water-soluble, mordant azophthalocyanine dyestuffs of the general formula COOH SO2.NH =N COOH and the alkali metal salts thereof, which A represents a substituted or unsubstituted metalliferous phthalocyanine molecule to which the SOz.O-, SO2.NH and SO3H groups are bound in the 3- or 4-positions, m represents H, halogen or CH3 bound in ortho-position to the SO2.O linkage, x representsH, CH3, OH, N02 or SO3H, y represents H, CH3 OCHs, SOaH or COOH jbound in ortho-position to the azo group, z represents H i or OCH3 bound in ortho-position to the SO2.NI-l

in which A represents a substituted or unsubstituted nited States Patent 2,776,958 Patented Jan. 8, 1957 metalliferous phthalocyanine molecule to which the SO Cl and SO H groups are bound in the 3- and 4-positions, and n represents a whole number from 1 to 4 is reacted with at least one molecular proportion of an amino-azo-dyestuff of the general formula N=N NHz HOOO in which x represents H, CH3, OH, N02 or SOsH, y represents H, CH3, OCm, SOsH or COOH bound in ortho-position to the azo-group, and z represents H or OCHs bound in ortho-position to the NHz group, and with at least one molecular proportion of a dihyd'roxybenzene carboxylic acid of the general formula COOH in which m represents H, halogen or CH3 bound in ortho-position to the reacting OH group, in an aqueous medium and in the presence of a substance capable of binding mineral acid, and the aforesaid reactions are carried out simultaneously or in either order of succession.

It has been unexpectedly found that the dyestuffs of the present invention are superior in their tinctorial properties to the dyestuffs of the aforesaid copending applications Serial Nos. 329,727 and 370,612. This superiority lies principally in the enhanced general properties of fastness of the dyestuffs of this invention. As compared with the dyestuffs of aforesaid copending application Serial No. 370,612, the dyestuffs of the present invention yield, especially in chrome printing, substantially purer green to olive tints.

Among the sulphochlorides of phthalocyanine tetrasulphonic acids suitable in the process of this invention there are included those which can be made by methods in themselves known. As phthalocyanine sulphochlorides suitable for the reaction there come into consideration more especially the sulphochlorides of copper-, nickelor cobalt-phthalocyanine, and also those of iron-, chromiumor aluminium phthalocyanine. Depending on the method used for preparing the sulphochloride, the sulphochloride groups are present in the phthalocyanine molecule in the 4- or 3positions, and this depends on whether they have been prepared by starting from 4-sulpho-phthalic acid, or whether the sulphochloride groups are introduced by sulphonation or by direct sulphochlorination of the phthalocyanine. The number of sulphochloride groups in the molecule may range from 1 to 4. In the preparation of the sulphochlorides of phthalocyan'ine tetrasulphonic acids, and especially in their isolation, there are generally obtained mixtures of phthaloc'yanines containing different numbers of sulphochloride groups.

Suitable amino-azo-dystuffs capable of taking part in the reaction are those of the general formula in which x, y and z have the meanings given above, and the NH2 group occupies a metaor para-position with respect to the azo linkage. As examples there may be mentioned:

3-amino-4'-hydroxy-l :1Fazobenzene-S-carboxylic acid 3 amino 2' methyl 4' hydroxy 1:1 azobenzene -carboxylic acid 3 amino 3' methyl 4' 5'-carboxylic acid 3 amino 4 hydroxy 1:1 azobenzene 5 carboxylic acid-G-sulphonic acid 3 amino 4 hydroxy 1:1 azobenzene 5' car boxylic acid-4-sulphonic acid 3 amino 4 methyl 4' hydroxy 1:1 azobenzene 5'-carboxylic acid 3 amino 6 methyl 4 hydroxy 1:1 azobenzene 5'-carboxylic acid 3 amino 6 methoxy 4' hydroxy 1:1 azobenzene 5-carboxylic acid 3 amino 2':4 dihydroxy 1:1 azobenzene 5 carboxylic acid 3 amino 6 chloro 4 hydroxy l :1' azobenzene 5 -carboxylic acid 4 amino 4 4 hydroxy 1:1 azobenzene 5' carboxylic acid 4 amino 2' methyl 4 hydroxy 1:1' azobenzene 5'-carboxylic acid 4 amino 3' methyl 4 hydroxy l :1 azobenzene 5-carboxylic acid 4 amino 4' hydroxy 1:1 azobenzene 5' carboxylic acid-S-sulphonic acid 4 amino 4 hydroxy 1:1 azobenzene 5' carboxylic acid-fi-sulphonic acid 4 amino 2 methyl 4 hydroxy 1:1 azobenzene- 5'carboxylic acid 4 amino 3 methyl 4' hydroxy 1:1 azobenzene- 5-carboxylic acid 4 amino 2 methyl 3 methyl 4 hydroxy 1:1

azobenzene-5'-carboxylic acid 4 amino 2 methoxy 4' hydroxy 1: 1 azobenzene 5-carboxylic acid 4 amino 3 methoxy 4' hydroxy 1:1 azobenzene 5-carboxylic acid 4 amino 3 ethoxy 4' hydroxy 1:1 azobenzeue 5-carboxylic acid 4 amino 2 methyl 5 methoxy 4' hydroxy 1:1

azobenzene5'-carboxylic acid 4 amino 2:5 dimethoxy 4 hydroxy 1:1 azobenzene-5'-carboxylic acid i 4 amino 2 chloro 4' hydroxy 1:1 azobenzene 5-carboxylic acid 4 amino 2 nitro 4' hydroxy 1:1 azobenzene 5'-carboxylic acid 4 amino 4' hydroxy 1:1 azobenzene 2:5 dicarboxylic acid 4 amino 2':4 dihydroxy 1:1 azobenzene 5 carboxylic acid 4 amino 2 methyl 3 chloro 4 hydroxy 1:1

azobenzene-5'-carboxylic acid 4 amino 2 methyl 3 nitro 4' hydroxy 1:1

azobenzenefi carboxylic acid 4 amino 2 methyl 5 methoxy 4 hydroxy 1:1

azchenzene-5'-carboxylic acid-3-sulphonic acid 4 amino 2 methyl 4' hydroxy 1:1 azobenzene 5'-carboxylic acid-3'-sulphonic acid 4 amino 3 methyl 4 hydroxy 1:1 azobenzene 5'-carboxylic acid-3-sulphonic acid 4 amino 2 bromo 4 hydroxy 1:1 azobenzene 5-earboxylic acid-6-su1phonic acid 4 amino 2:6 dibrom 4 hydroxy 1:1 azobenzene-5-carboxylic acid 4 amino 2 methyl 5 methoxy 2' hydroxy l :1

azobenzene'y-carboxylic acid 4 amino 3 methyl 2' hydroxy 1:1 azobenzene 3'-carboxylic acid-5-sulphonic acid 4 amino 2 methyl 5 methoxy 5 nitro 2 hydroxy-l: 1-azobenzene-3-carboxylic acid hydroxy 1:1 azobenzene 4 amino 2 methyl 3 hydroxy 1:1 azobenzcne 4-carboxylic acid 4 amino 3 methyl 3 hytlroxy 1:1" azobenzene 4-carboxylic acid.

Suitable dihydroxy-benzene carboxylic acids capable of taking part in the reaction are, for example, 1:4-dihydroxybenzene-5-carboxylic acid (gentisic acid), 3-chloro 1 z4-dihydroxybenzene-5-carboxylic acid, 3-bromo-1c4-dihydroxybenzene-S-carboxylic acid, 3-methyl-1:4-dihydroxybenzene 5 carboxylic acid, 1:4 dihydroxybenzene 5- carboxylic acid-3-sulphonie acid, 1:3-dihydroxybenzene- 4-carb0xylic acid (fi-resorcylic acid), 6-chloro-1:3-dihydroxybenzene-4-carboxylic acid, 6-bromo-1z3-dihydroxybenzene-4-carboxylic acid, S-methyl-l:3-dihydroxybenzene-4-carboxylic acid, 1 :2 3-trihydroxybenzene-4-carboxylic acid (pyrogallolcarboxylic acid), 1:2-dihydroxybenzene-3-carboxylic acid, 1:2-dihydroxybenzene-3-carboxylic acid-S-sulphonic acid and the like.

The reaction of the sulphonic acid chlorides of the phthalocyanine sulphonic acids with the amino-azo-dyestuds and the dihydroXy-benzene carboxylic acids is carried out in an aqueous medium and in the presence of at least one substance capable of binding a mineral acid such, for example, as an alkali hydroxide, alkaline earth metal hydroxide, an alkali carbonate, an alkaline earth metal carbonate, an alkali bicarbonate, magnesium oxide, sodium acetate, ammonia, ammonium carbonate, di methyl-formamide, triethanolamine, pyridine or the like.

The reactions of the sulphochloride with the aminoazodyestutf and with the dihydroxybenzene carboxylic acid may be carried out simultaneously or in either order of succession.

The reaction temperature is of minor importance and may vary within very wide limits, but it is of advantage to work at low temperatures, advantageously, at temperatures Within the range of 0 C. to 30 C.

Depending on the choice of the reaction temperature and the substance capable of binding mineral acid, hydrolysis of the sulphochloride groups during the reaction, which can never be entirely avoided, can he suppressed to a greater or less extent. It is not absolutely necessary that all the sulphochloride groups should react with the aminoazo-dyestuff and the dihydroxybenzene carboxylic acid. It is often of advantage, especially with regard to its solubility, that the dyestutf should still con tain one or two snlpho-groups.

The various sulphochlorides used in the process of the invention are reacted with at least one molecular proportion of the aminoazo-dyestuff and at least one molecular proportion of a dihydroxybenzene carboxylic acid. Thus, one mol of phthalocyanine tetrasulphochloride may be reacted with one mol of aminoazo-dyestuif and with one mol or two mols of a dihydroxybenzene carboxylic acid, or with two mols of aminoazo-dyestulf and one mol of a dihydroxybenzene-carboxylic acid, or with three mols of aminoazo-dyestuff and with one mol of a dihydroxybenzene carboxylic acid, or with 1 mol of aminoazodyestuff and with three mols of a dihydroxybenzene carboxylic acid, or with two mols of aminoazo-dyestufi and with two mols of a dihydroxybenzene carboxylic acid.

The invention also includes reacting the sulpochloride of the phthalocyanine tetrasulphonic acid with a mixture of at least two aminoazo-dyestutfs and a dihydroxybenzene carboxylic acid of the above general formulae, or with a mixture of at least two dihydroxy-benzene carboxylic acids and an aminoazo-dyestuff or with a mixture of two aminoazo-dyestulfs and two dihydroxybenzene carboxylic acids.

It is not certain in all cases Whether the sulphochloride groups are wholly or only partially converted into sulphonic acid amide groups and ester groups in accordance with the invention.

Depending on the choice of the phthalocyanine sulphochloride used and on the number of mols of aminoazodyestufi (1-3) and of dihydroxybenzene carboxylic acid 5 (3-1 used for the reaction, there are obtained dyestuffs having different tinctorial properties. I

Owing to the presence of at least two salicylic acid groups in the dyestuff molecule, it is possible to fix the dyestuff on the fibre in the form of a chromium lake by known methods. The new dyestuffs are especially suit.- able for chrome printing on cotton. The mordant character of the phthalocyanine dyestuffs of the invention increases as the number of salicylic acid groups increases, which is quite evident from the progressive improvement in the properties of wet fastness. Green to olive tints are produced which are distinguished by their very good to excellent general properties of fastness.

Moreover, the new dyestuffs, when they contain suflicient mordanting groups, can be fixed on textile fibres by after-treatment by known methods with agents yielding metal, especially in conjunction with basic substances of high molecular weight. Green to olive dyeings which are distinguished by their good fastness to Washing and light are produced, more especially, by after-treating prints on cellulose fibres or fibres of regenerated celluloses with an agent yielding copper together with a basic condensation product of high molecular weight.

The alkali salts of the azo-phthalocyanine dyestuffs of the invention are easily soluble in water, and are suitable for dyeing and printing vegetable, animal and wholly synthetic fibres, and also for dyeing oxidic protective coatings on aluminium. Especially valuable are the dyestuffs described in the succeeding Examples 2 (fourth para-- graph), 3, 12, 26 and 28.

The following examples illustrate the invention, the parts being by weight:

Example I 96.9 parts mol) of freshly prepared copper phthalocyanine tetrasulphochloride (obtained by the action of chlcrosulphonic acid on copper phthalocyanine) are poured on to ice, and the precipitated reaction product is mixed in the form of a moist paste with 350 parts of crushed ice. There is then rapidly added, while stirring, a cold solution of 27.9 parts mol) of the sodium salt of 3-amino-4-hydroXy-1:1-azobenzene-5'-carboxylic acid and 59.4 parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid in 600 parts of water, to which 20 parts of calcium carbonate have been added, and the whole is stirred for 5 hours at 5-10" C. and for a further 24 hours at room temperature. When the reaction is finished, the mixture is rendered weaklyacid with dilute hydrochloric acid, and the precipitated dyestufi acid is filtered off with suction and washed with dilute hydrochloric acid. It is then dissolved in water and sodium carbonate, and the dyestuff is isolated in the form of its sodium salt by salting out with sodium chloride from a weakly alkaline medium.

The dyestulf so obtained is a green powder which dis solves in water with a blue-green coloration and in concentrated sulphuric acid with a yellow-green coloration.

When used for chrome printing on cotton the dyestuff yields a deep yellowish green tint having excellent properties of fastness.

By using 55.8 parts mol) of the sodium salt of 3- aniino-4'-hydroxyl l-azobenzene-5-carboxylic acid, instead of 27.9 parts mol) thereof, and 39.6 parts mol) of the disodium salt of 1:3-dihydroxybenzenel-carboxylic acid, instead of 59.4 parts mol) there of, there is obtained a dyestuff which yields in chrome printing on cotton a grass green tint having excellent properties of wet fastness and an excellent fastness to light. The dyestufi is also suitable for dyeing oxidic protective coatings on aluminium, whereby a pure bluegreen tint is produced.

By using 83.7 parts mol) of the sodium salt of 3- amino-4'-hydroxy-1 1'-azobenzene-5-carboxylic acid, instead of 55.8 parts (91 mol) thereof, and 19.8 parts mol) of the disodium salt of l:3-dihydroxyb enzene 4-carboxylic acid, instead of 39.6 parts mol) thereof,

there is obtained a dyestutf suitable for dyeing cotton and viscose. A powerful blue green tint is produced on prechromed cotton. The dyestuif is especially suitable for chrome printing on cotton. There are obtained blue-green prints having good properties of wet fastness and very good fastness to light.

Example 2 96.9 parts mol) of freshly prepared copper phthalocyanine-4z4:4":4"-tetrasulphochloride, obtained by the action of chlorosulphonic acid on copper phthalocyanine- 4:4:4":4"'-tetrasulphonic acid (obtained from 4-sulphophthalic acid), are discharged on to ice and the precipitated reaction product is mixed in the form of a moist paste with 350 parts of disintegrated ice. There is rapidly added, while cooling, a cold solution of 27.9 parts mol) of the sodium salt of 3-amino-4'-hydroxy-1:1- azobenzene-5'-carboxylic acid and 59.4 parts A mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid in 600 parts of water, to which 15 parts of calcium carbonate have been added. The whole is stirred for 3-4 hours at 510 C., and for a further 48 hours at room temperature. When the reaction is finished, the mixture is rendered acid (pH=3) to Congo by the addition of dilute hydrochloric acid, and the precipitated dyestuff acid is separated and converted into its sodium salt.

The dyestuif so obtained is a dark violet powder which dissolves in water with a turquoise blue coloration and in concentrated sulphuric acid with a yellow green coloration.

The dyestuif is suitable for dyeing cotton, viscose, nylon and wool. By after-chroming the dyeings there are ob tained on wool bluish green tints and on cotton powerful blue-green tints, which are distinguished by their good properties of wet fastness and very good fastness to light. The dyestuff is especially suitable for chrome printing on cotton. It yields a bright deep blue-green tint having excellent properties of fastness and an outstanding fastness to light. The dyestutf is also suitable for dyeing oxidic protective coatings on aluminium.

By using 55.8 parts mol) of the sodium salt of 3-amino-4'-hydroxy-1 1'-azobenzene-5-carboxylic acid, instead of 27.9 parts mol) thereof, and 39.6 parts 4 mol) of the disodium salt of 1:3-di'hydroxybenzene- 4-carboxylic acid, instead of 59.4 parts A mol) thereof, there is obtained a dyestuff of the formula COONa which is a derivative of copper-phthalocyanine-4,4',4, 4"'-tetrasulphonic acid, and yields in chrome printing on cotton, green tints possessing outstanding properties of wet fastness and an excellent fastness to light.

By using 83.7 parts )5 mol) of the sodium salt of 3 amino 4' hydroxy 1:1 azobenzene 5' carboxylic acid, instead of 55.8 parts mol) thereof, and 19.8 parts (M mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid, instead of 39.6 parts mol) thereof, there is obtained a dyestuif which yields in chrome printing on cotton bright deep yellow green tints having very good propeities of wet fastness and an excellent fastness to light.

Example 3 96.9 parts A mol) of copper phthalocyanine' tetrasulphochloride, obtained as described in Example 1, are stirred in 350 parts of ice to form a homogeneous paste. There is then added, while stirring, a solution of 39.6

. sat-6155a parts @1 mol) of the disodium salt of 1:3-dihydroxy' benzene-4-carboxylic acid in 200 parts of ice water (Solution I), and the whole is stirred for one hour. There is then rapidly added a solution of 27.9 parts (31 moi) of the sodium salt of 3-amino-4'-hydroxy-1:1-azobenzene- -carboxyiic acid in 250 parts of water (solution II), to which parts of calciumcarbonate have been added, and the whole is stirred for 24 hours at 20 C. When the reaction is finished, the mixture is rendered acid (Pb-=3) to Congo with dilute hydrochloric acid, and the precipitated dyestutf acid is separated off and dissolved in water and sodium carbonate, and the dyestuff is salted out with sodium chloride.

The dyestuit so obtained corresponds to the formula i SOz.O'COONa COOK-a is a derivative of copper-phthalocyanine-3,3,3,3"-tetrasulphonic acid, and is a. blue-green powder which dissolves in water with a blue coloration and in concentrated sulphuric acid with a yellow-green coloration.

In chrome printing on cotton the dyestuft yields deep grass green tints having very good properties of wet tastness and an excellent fastness to light.

By first using solution ll, instead of solution I, stirring the mixture for one hour, and then adding solution I, there is obtained a dyestuff which is identical with the dyestuff described above. By adding solution I and Il simultaneously (a mixture) the same dyestut't is also obtained.

Example 4 48.5 parts moi) of copper phthalocyanine tetrasulphochloride is obtained as described in Example 1, are mixed with 200 parts of ice, and there is rapidly added while stirring a solution of 9.8 parts moi) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 14 parts moi) of the sodium salt of 3-amino-4'- hydroxy-l:1'-azobenzene-5-carboxylic acid in 350 parts of ice water, to which 10 parts of calcium carbonate have been added, and the whole is stirred for 2 hours at room temperature and for a further two hours at 70 C. When the reaction is finished, the mixture is rendered weakly acid (pl-i=3) to Congo with dilute hydrochloric acid, and the precipitated dyestufi acid is separated off, dissolved in water and sodium carbonate, and the dyestufi' is salted out with sodium chloride.

The dyestufi so obtained is a dark blue-green powder, which dissolves in water with a greenish blue coloration and in concentrated sulphuric acid with a yellow-green coloration.

By acid dyeing on wool there is produced a blue-green tint, which is converted into a deep green by after-chroming. The dyestufi yields on viscose and cotton bluegreen tints and on prechromed cotton powerful green tints. It dyes anodically oxidised aluminium blue-green tints.

In chrome printing on cotton it yields clear grass green tints having good properties of fastness.

Example 5 of 12.9 parts & mol) of 3-arnino-4'-hydroxy-l:lf-azobenzene-5'-carboxylic acid, 7.8 parts fi moi) of 1:3-

dihydroxybenzene-4-carboxyiic acid and 12.5 parts of sodium hydroxide in 500 parts of water, and the whole is stirred for 14 hours. When the reaction is finished, the dyestuff is salted out with 180 parts of sodium chloride and isolated in the form of its sodium salt.

The dyestuft so obtained is a blue-green powder which dissolves in water with a blue coloration and in concentrated sulphuric acid with a yellow-green coloration.

In chrome printing on cotton it yields bluish-green tints having good properties of wet fastness and very good fastness to light.

Example 6 44.8 parts ,5 moi) of copper phthaloeyanine tetrasulphonic acid, obtained by the sulphonation of copper phthalocyanine with oleurn of 14 percent strength, are converted into the copper phthalocyanine tetrasulphochloride by means of chlorosulphonic acid and thionyl chloride, the reaction mixture is discharged on to ice and water, the press cake, after being washed with an aqueous solution of sodium chloride, is stirred in 200 parts of disintegrated ice to form a homogeneous paste, and the latter is added to a cold solution of 25.7 parts of 3 amino 4' hydroxy 1:1 azobenzene 5 carboxyiic acid moi), 7.8 parts of 1:3-dihydroxybenzene-4-carboxylic acid moi) and 19 parts of sodium hydroxide (100%) in 450 parts of water. The whole is stirred for 24 hours and, after the reaction, the dycstuti is salted out with 180 parts of sodium chloride. The dyestuff is purified by being salted out twice. The dyestuff so obtained is a green powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with a yellow-green coloration.

In chrome printing on cotton it yields strong green tints having very good properties of fastness.

Example 7 48.5 parts A moi) of copper phthalocyaninc tetrasulphochloride, obtained as described in Example 1, are discharged on to ice and the separated reaction product is well mixed in the form of a moist paste with 250 parts of ice, and there is rapidly added a cold solution of 19.8 parts moi) of the disodium salt of 1:3dihydroxybenzene'4-carboxylic acid and 14.7 parts (V10 moi) of. the sodium salt of 4-amino-3'-methyl-4'-hydroxy-l :1- azobenzene-5'-carboxylic acid in 450 parts of water, to which 5 parts of calcium carbonate have been added, and the whole is stirred for 24 hours at room temperature. After acidifying the mixture with dilute hydrochloric acid, the precipitated dyestuflf acid is separated off and converted into its sodium salt.

The dyestuff so obtained is a blue-green powder which dissolves in water with a greenish-blue coloration and in concentrated sulphuric acid with an olive coloration.

In chrome printing on cotton it yields clear bluegreen tints having good properties of wet fastness and a good fastness to light.

Example 8 29 parts i moi) of copper phthalocyanine tetrasulphochloride, obtained as described in Example 1, are mixed with parts of crushed ice, and there are rapidly added while stirring, in an atmosphere of nitrogen a solution of 11.8 parts (fi moi) of the disodium salt of l:4-dihydroxybenzeneS-carboxylic acid and 8.9 parts 7 moi) of the sodium salt of 4-amino-2':4-dihydroxy- 1:1'-azobenzene-5-carboxylie acid in 300 parts of water, to which 5 parts of calcium carbonate have been added. The whole is stirred for 10 hours at 5l0 C., and for a further 15 hours at room temperature. The dyestuif is isolated in the manner described in Example 1.

The dyestuif so obtained is a dark grey powder which dissolves in water with a green coloration and in concentrated sulphuric acid with an olive coloration.

In chrome printing on cotton it yields dark olive green tints having good properties of fastness.

9 Example 9 96.9 parts mol) of freshly prepared copper phthalocyanine tetrasulphochloride, obtained by the action of chlorosulphonic acid on copper phthalocyanine, are discharged on to ice and the separated reaction product is mixed in the form of a moist paste with 350 parts of crushed ice. There is rapidly added, while stirring, a cold solution of 39.6 parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 76.2 parts mol) of the disodium salt of 4-amino-4- hydroxy-l l-azobenzene-5 -carboxylic acid-6-sulphonic acid in 600 parts of Water, to which has been added 20 parts of calcium carbonate. The Whole is stirred for 30 hours at 2025 C., and after the reaction, the mixture is rendered weakly acid with hydrochloride acid, the precipitated dyestuff acid is sep rated off, dissolved in water and sodium carbonate, and the dyestuff is isolated by salting out with sodium chloride.

The dyestuff so obtained is a blue-black powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with a brown coloration.

By acid dyeing on Wool it yields pure yellowish green tints, and olive tints upon after-chroming. By dyeing on prechromed cotton there are produced deep strong grass green tints, and on nylon yellow-green tints and on viscose greenish-blue tints.

In chrome printing on cotton there are obtained yellow green tints having good properties of wet fastness and a very good fastness to light.

Example 10 48.5 parts (V mol) of copper phthalocyanine tetrasulphochloride, obtained as described in Example 1, are stirred to form a homogeneous paste with 250 parts of ice Water, and the mixture is added to a solution of 9.9 parts mol) of the disodium salt of 1:3-dihydroxy benZene-4-carboxylic acid, 42.5 parts mol) of the disodium salt of 4-amino-2-methyl-5-methoxy-4-hydroxy- 1:l'-azobenzene-5'-carboxylic acid-3'-sulphonic acid and 5 parts of sodium carbonate in 500 parts of water, and the whole is stirred for 24 hours at C. The sodium salt of the dyestuif is isolated in the usual manner.

The dyestufi so obtained is an olive powder which dis solves in water with a green coloration and in concentrated sulphuric acid with a pink coloration.

In chrome printing on cotton the dyestuif yields yellow green tints.

Example 1] 48.5 parts mol) of copper phthalocyanine tetrasulphochloride, obtained as described in Example 1, are mixed with 250 parts of ice, and rapidly added to a solution of 30.9 parts 4 mol) of the dipotassium salt of 6-bromo-1:3-dihydroxybenzene-4-carboxylic acid and 14.6 parts & mol) of the sodium salt of 4-amino-2- methyl-4'-hydroxy-1: 1-azobenzene-5'-carboxylic acid in 500 parts of water, to which 8 parts of calcium carbonate have been added, and the whole is stirred for 24 hours at 20 C. The dyestuif is isolated in the manner described in Example 1.

The dyestufi so obtained is a grey-olive powder which dissolves in water with a green coloration and in concentrated sulphuric acid with a dirty orange coloration.

In chrome printing on cottonthe dyestulf yields yellowgreen tints having good properties of fastness.

Example 12 96.9 parts mol) of freshly prepared copper phthalocyanine tetrasulphochloride (crude product), obtained by the action of chlorosulphonic acid on copper phthalocyanine, are discharged on to ice, and the precipitated reaction product is mixed in the form of a moist paste with 300 parts of broken ice. There is then rapidly added, while stirring, a solution of 30.9 parts A mol) of the dipotassium salt of 6--bromo-1:3-dihydroxyben:

zene-4-carboxylic acid, 59 parts mol) of the po tassium salt of 3-amino-4'-hydroxy-l:1-azobenzene-5- carboxylic acid and 15 parts of potassium hydroxide in 600 parts of water, and the whole is stirred for 10 hours at 540 C. and for a further 5 hours at room temperature. When the reaction is finished, the whole is rendered weakly acid with dilute hydrochloric acid, the precipitated dyestufi acid is separated ofii', the latter is dissolved in water and potassium carbonate and the dyestufi' is salted out from the weakly alkaline medium with potassium chloride.

The dyestuff so obtained corresponds to the formula wow-Quoom COONa i l somn- N=NOH Example 13 48.5 parts mol) of copper phthalocyanine tetrasulphochloride, obtained as described in Example 1, are discharged on to ice, the reaction product is separated and mixed with 200 parts of ice, and the whole is rapidly added, while stirring, to a solution of 23.0 parts mol) of the dipotassium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 41.3 parts mol) of the dipotassiurn salt of 3-amino-4'-hydroxy-l l'-azobenzene-5 '-carboxy1ic acid-6-sulphonic acid in 400 parts of water, to which 10 parts of calcium carbonate have been added, and the whole is stirred for 24 hours at 1()20 C. The dyestutf is isolated as described in Example 11.

The dyestufi so obtained is a blue-green powder which dissolves in water with a blue coloration and in concentrated sulphuric acid with a yellow-green coloration.

In chrome printing on cotton the dyestuif yields grass green tints having good properties of fastness.

Example 14 48.5 parts mol) of copper pl1thalocyanine-4:4':4: 4'-tetrasulphochloride (obtained as described in Example 2), are discharged on to ice, and the separated reaction product in the form of a moist paste is mixed Well with 250 parts of broken ice, and the whole is rapidly added to an ice-cold solution of 19.8 parts A mol) of the disodium salt of 1:3-dihydroxybenzene-4- carboxylic acid and 42.5 parts A mol) of the disodium salt of 4-arnino-2-methyl-5-methoxy-4'-hydroxy-1 l azobenzene-5'-carboxylic acid-3-su1phonic acid in 350 parts of Water, to which has been added 10 parts of calcium carbonate. The whole is stirred for 48 hours at 1520 C. The dyestuif is isolated as described in EX- ample 8.

Example 15 485 parts mol) of copper phthalocyanine-4z4'z4": 4tetrasulphochloride are treated in a manner analogous to that described in Example 2, and the paste so obtained is mixed with a cold solution of 9.9 parts mol) of. the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 44 parts G mol) of the sodium salt of 4-amino- 2-rnethyl-4'-hydroxy-l: 1-azobenzene-5-carboxylic acid in 400 parts of water, to which have been added 10 parts of calcium carbonate, the whole is stirred for 48 hours at room temperature. When the reaction is finished, the mixture is rendered Weakly acid (pH=3) to Congo with dilute hydrochloric acid, and the precipitated dyestufi acid is converted in the usual manner into its sodium salt.

The dyestuff so obtained is a dark green powder which dissolves in water with a green coloration and in concentrated sulphuric acid with a dirty orange coloration.

In chrome printing on cotton the dyestutf yields yellowgreen tints having excellent properties of wet fastness and a good fastness to light.

Example 16 29 parts ([1 1] mol) of a copper phthalocyanine-4z4: 4":4-tetrasulphochloride, obtained as described in Example 2. are mixed with 150 parts of ice, and the whole is rapidly added while stirring to an ice-cold solution of 11.9 parts 73 mol) of the disodium salt of 1:3-dihydroxybenzcnel-carboxylic acid, 17.7 parts (fi mol) of the sodium salt of 4amino-2:4'-dihydroxy-l:l-azobenzene-5'-carboxylic acid and 8 parts of sodium acetate in 400 parts of water at O-5 C. The whole is stirred at that temperature for 5 hours and then for a further 40 hours at room temperature. The dyestuff is isolated as described in Example 14.

The dyestuil so obtained is a blue-violet powder which dissolves in water with an olive coloration and in con centrated sulphuric acid with an olive green coloration.

In chrome printing on cotton the dyestutf yields olive tints having very good properties of wet fastness and a 7 moderate fastness to light.

Example 17 43.5 parts /30 mol) of freshly prepared copper phthalocyanine-4 4 4" 4"-tetrasulphcchloride (obtained as described in Example 2), are discharged on to ice and the separated reaction product is mixed in the form of a moist paste with 200 parts of ice, and the Whole is rapidly added while stirring, to a cold solution of 9.9 parts (/30 mol) of l:4-dihydroxybenzene-S-carboxylic acid (disodium salt) and 38.1 parts A mol) of the disodium salt of 3amino-4-hydroxy-1:l-azobenzene-5- carboxylic acid-6-sulphonic acid (obtained by the reaction of 3-nitraniline-6-sulphonic acid with salicylic acid, and then reducing the nitro group with sodium sulphide) in 300 parts of water, to which 10 parts of calcium carbonate have been added. The whole is stirred at room temperature for 48 hours. The dyestutf is separated by acidification With dilute sulphuric acid and converted into its sodium salt.

The dyestuff so obtained is a dark violet powder which dissolves in water with a bluish green coloration and in concentrated sulphuric acid with a yellow-brown coloration.

12 The dyestufl? is suitable for chrome printing on cotton and yields green tints having good properties of fastness. Instead of the sodium salt, there may be used the potassium or lithium salt.

Example 18 48.5 parts mol) of freshly prepared copper phthalocyanine-4:4:4":4-tetrasulphochloride obtained as described in Example 1, are mixed as described in Example 2 with 200 parts of ice, and rapidly added in an atmosphere of nitrogen to a solution of 11.8 parts & mol) of 1:2:3-trihydroxybenzene-4-carboxylic acid (trisodium salt) and 27.9 parts mol) of the sodium salt of 3-amino-4'-hydroxy-1:1-azobenzene-5'-carboxylic acid in 400 parts of. water, to which 15 parts of magnesium oxide have been added. The whole is then stirred for 10 hours at 05 C. and for a further 30 hours at room temperature. When the reaction is finished, the product is worked up in the usual manner and the sodium salt of the dyestuif is isolated.

The dyestufi so obtained is a dark violet powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with a yellow-green coloration.

In chrome printing on cotton the dyestufi yields bluegreen tints having excellent properties of wet fastness and a good fastness to light.

Example 19 48.5 parts mol) of copper phthalocyanine- 4:4:4":4-tetrasulphochloride, obtained as described in Example 2, are discharged on to ice, the separated reaction product is mixed with 250 parts of ice, and the whole is rapidly added while stirring at 10 C. to a solution of 46.4 parts GA mol) of the dipotassium salt of 6-bromol:3-dihydroxybenzene-4-carboxylic acid and 14.7 parts mol) of the sodium salt of 4-amino-3-methy]-4'- hydroxy-l:l'-azobehzene-5-carboxylic acid in 350 parts of water, to which has been added 10 parts of magnesium carbonate. The whole is stirred for 50 hours at room temperature. After acidification with dilute hydrochloric acid, the precipitated dyestuff acid is separated off and converted into its sodium salt in the usual manner.

The dyestuff so obtained is a blue-violet powder which dissolves in water with a bright blue-green coloration and in concentrated sulphuric acid with a yellow-brown coloration.

In chrome printing on cotton, the dyestuff yields deep blue-green tints having remarkable properties of wet fastness and an excellent fastness to light.

Example 20 485 parts 20 mol) of freshly prepared copper phthalocyanine-4z4'z4:4"-tetrasulphochloride, obtained as described in Example 2, are discharged on to ice, and the reaction product is mixed in the form of a moist paste with 250 parts of ice, and rapidly added in an atmosphere of nitrogen, while stirring, to an ice-cold solution of 19.8 parts mol) of the disodium salt of 1:4-dihydroxybenzene-5-carboxylic acid and 14 parts mol) of the sodium salt of 4-amino-4'-hydroxy-l :1'-azobenzene-5- carboxylic acid in 350 parts of ice water, to which have been added 10 parts of sodium bicarbonate. The whole is stirred for 10 hours at 510 C. and then for 30 hours at room temperature. The dyestulf is separated by acidification with dilute hydrochloric acid and converted into its sodium salt.

The dyestutf so obtained is a blue-violet powder which dissolves in water with a blue green coloration and in concentrated sulphuric acid with a green coloration.

The dyestuff dyes oxidic protective coatings of aluminimum olive green tints. In chrome printing on cotton the dyestuff yields green tints having excellent properties of fastness. I

13 Example 21 48.5 parts & mol) of copper phthalocyanine- 4:4:4:4"'-tetrasulphochloride, obtained as described in Example 2, are mixed with 200 parts of broken ice, and there is added, while stirring, a cold solution of 10.6 parts mol) of the disodium salt of 3-methyl-1z4-dihydroxybenzene-S-carboxylic acid, 57.2 parts mol) of the disodium salt of 4-amino-4hydroxy-1:1'-azobenzene-5- carboxylic acid-G-sulphonic acid and 6 parts of triethanolamine in 300 parts of water, and the whole is stirred for 48 hours at 15-20 C. When the reaction is finished the dyesturl is separated in the form of its sodium salt as desciibed in Example 18.

The dyestulf so obtained corresponds to the formula 30 ONa 402.0001: 6H.

(IJOONa E soiNn-Qmrrgoia SOItN s is a derivative of copper-phthalocyanine-4,4,4",4"-tetrasulphonic acid, and is a blue violet powder which dissolves in Water with a green coloration and in concentrated sulphuric acid with a grey brown coloration.

In chrome printing on cotton the dyestuff yields olive green tints.

Example 22 carboxylic acid in 1000 parts of water, to which have been added 10 parts of calcium carbonate. The whole is stirred for 55 hours at 15-20 C. By acidifying the reaction mixture the dyestuif acid is precipitated, and the latter is converted into its sodium salt in the usual manner.

The dyestufi so obtained is a dark violet powder which dissolves in water with a green coloration and in concentrated sulphuric acid with a brown-red coloration.

In chrome printing on cotton deep olive green tints are produced.

Example 23 48.5 parts mol) of freshly prepared copper phthalocyanine-4z4':4":4"-tetrasulphochloride, obtained as described in Example 2, are discharged on to ice and the separated reaction product is mixed as a moist paste with 200 par-ts of ice. The whole is rapidly added, while stir- The whole acid, the precipitated dyestufi acid is separated oil and the latter is converted into its sodium salt.

14 The dyestufi' so obtained corresponds to the formula COONa OOONa is a derivative of copper-phthalocyanine-4,4,4",4'-tetrasulphonic acid, and is a dark violet powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with an olive coloration.

In chrome printing on cotton the dyestuff yields grass green tints having excellent properties of wet fastness and a remarkable fastness to light.

Example 24 48.5 pants mol) of copper phthalocyanine- 4:4:4":4'tetrasulphochloride (obtained as described in Example 2) are discharged on to ice, and the separated reaction product is mixed with 200 parts of ice. The whole is rapidly added, while stirring, to a cold solution of 19.8 parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 14 parts mol) of the sodium salt of 3-arnino-4-hydroxy-1:1-azobenzene- 5-carboxylic acid and 19 parts mol) of the disodium salt of 3-amino-4-hydroxy-1:1'-azobenzene-5-carboxylic Example 25 485 parts mol) of copper phthalocyanine- 4:4:4:4"'-tetrasulphochloride, obtained as described in Example 1, are discharged on to ice, the separated reaction product is mixed with 200 parts of ice, and the Whole is rapidly added While stirring, to an ice-cold solution of 9.9 parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid, 9.9 parts mol) of the disodium salt of l:4-dihydroxybenzene-5-carboxylic acid, and 14 parts mol) of the sodium salt of 3-amino-4-hydroXy-l:l-azobenzene-5-carboxylic acid and 15.5 parts A mol) of the sodium salt of 3-amino-6-methoxy-4- hydroxy-l:1-azobenzene-5'-carboxylic acid in 500 parts of water, to which have been added 10 parts of calcium carbonate. The whole is stirred for 48 hours at room temperature. After acidifying the reaction mixture with dilute hydrochloric acid the dyestuff acid is separated oil and converted into its sodium salt in the usual manner.

The dyestufi so obtained is a dark violet powder which dissolves in water with a blue green coloration and in concentrated sulphuric acid with a brown coloration.

In chrome printing on cotton the dyestuff yields yellowish green tints having very good properties of wet fastness and of excellent fastness to light.

Example 26 56.4 parts 4 mol) of brominated copper phthalocyamine-4:4:4,:4'-tetrasulphochlo1ide, obtained by the action of chlorosulphonic acid on the tetrasodium salt of 15 brominated copper phthalocyanine-4z4:4":4"-sulphonic acid (containing 11.5 percent of bromine by analysis), are discharged on to ice, and the separated reaction product is mixed with 300 parts of broken ice. The whole is rapidly added, while stirring, to a solution of 19.8 parts mol) of the disodium salt of 1:3-dihydroxybenzene 4-carboxylic acid and 14 parts mol) of the sodium salt of 3-amino-4'-hydroxy-l:l'azobenzene-S'-carboxylic acid in 300 parts of water, to which have been added parts of calcium carbonate. The Whole is stirred at room temperature for 48 hours and the dyestutr is isolated in the form of its sodium salt.

The dyestuff so obtained corresponds to the formula I somOooom COONa S OgNa Example 27 96.5 parts A mol) of freshly prepared cobalt phthalocyanine tetrasulphochloride, obtained by the action of chlorosulphonic acid on cobalt phthalocyanine, are dis charged on to ice and the separated reaction product is mixed in the form of a moist paste with 350 parts of broken ice. The whole is rapidly added to a solution of 19.8 par-ts A mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 61.8 parts mol) of the sodium salt of 3-amino-6-methoxy-4'-hydroxy-l:1- azobenzene-S'-carboxylic acid in 600 parts of water, to which have been added parts of calcium carbonate. The mixture is stirred for 26 hours at 1520 C. The sodium salt of the dyestuit is isolated as described in Example 24.

The dyestuii so obtained is a blue-green powder which dissolves in water with a blue green coloration and in concentrated sulphuric acid with a dark grey coloration.

In chrome printing on cotton the dyestuif yields green tints having very good properties of fastness.

Example 28 96.5 parts mol) of freshly prepared cobalt phthalo cyanine-4:4:4":4"-tetrasulphochloride, obtained by the reaction of chlorosulphonic acid with cobalt phthalocyaninc-4z4:4:4"-tctrasulphonic acid, are discharged on to ice and the separated reaction product is mixed in the form of a moist paste with 350 parts of broken ice. There is rapidly added a solution of 59.4 parts i mol) of the disodium salt of l:3-dihydroxybenzenelb The dyestuff so obtained corresponds to the formula I E SOLO-O0 o ONa OOONa SO:.NH N=N- 0H.

OOHa

Example 29 48.2 parts A mol) of nickel phthalocyanine tetrasulphochloride, obtained by the action of chlorosulphonic acid on nickel phthalocyanine, are discharged on to ice and the separated reaction product is mixed as a moist paste with 200 parts of ice. The whole is rapidly added to a solution of 19.8 parts 4 mol) of the disodium salt of l:3-dihydroxybenzene-4-carboxylic acid and 27.9 parts mol) of the sodium salt of 3'amino-4-hydroxy-l:l-azobenzene-5'-carboxylic acid irr450 parts of water, to which have been added 10 parts of calcium carbonate. The whole is stirred for 24 hours at 20 C. When the reaction is finished, the mixture is rendered weakly acid to Congo with dilute hydrochloric acid, and the dyestutf acid is separated off and isolated as its sodium salt.

The dyestutl obtained is a green powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with a yellow-green coloration.

In acid dyeing on wool the dyestuif yields blue-green tints which become full green blue tints when afterchromed. In dyeing on pre-chromed cotton the dyestuff yields strong blue green tints, which is also the case in direct dyeing on viscose. The dyestufl? is especially suitable tor chrome printing on cotton, whereby deep bright grass green tints having excellent properties of wet fastness and a remarkable fastness to light are obtained.

Example 30 96.4 parts mol) of nickel phthalocyanine- 4:4:4":4"'-tetrasulphochloride, obtained by the action of chlorosulphonic acid on nickel phthalocyanine-4:4:4:- 4"-tetrasulphonic acid, are mixed well with 350 parts of ice. The whole is rapidly added, while stirring, to a solution of 61.8 parts mol) of 6-bromo-1z3-dihydroxybenzenel-carboxylic acid (dipotassium salt) and 75.4 parts (3 mol) of the dipotassium salt of 4-amino- 4-hydr0xy-l:l-azobenzene-2:5'-dicarboxylic acid in 650 parts of water, to which have been added 15 parts of calcium carbonate. The whole is stirred for 50 hours at 1520 C. When the reaction is finished the reaction mixture is rendered weakly acid with dilute hydrochloric acid, the precipitated dyestulf acid is separated oil, and the latter is dissolved in water and sodium carbonate, and the dyestulf is salted out.

The dyestuit so obtained is a dark. violet powder which dissolves in water with a blue coloration and in concentrated sulphuric acid with an olive coloration.

In chrome printing on cotton the dyestuif yields deep blue green tints having very good properties of fastness.

Example 31 47.9 parts mol) of chromium phthalocyanine tetrasulphoch-loride,. obtained bythe action of chlorosulphonic acid on chromium phthalocyanine, are discharged on to ice and the separated reaction product is stirred as a moist paste with 200 parts of cold water to form a homogeneous paste. The latter is rapidly added to a solution, heated at 4050 C., or" 19.8parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 14 parts mol) of the sodium salt of 4- amino-4-hydroxy-l:1-azobenzene-5-carboxylic acid in 450 parts of water, to which have been added 10 parts of calcium carbonate, and the whole is stirred for 6 hours at 45 C. When the reaction is finished, the reaction mixture is acidified and the dyestuif acid is precipitated with dilute hydrochloric acid, separated off, and converted into its sodium salt.

The dyestufl? so obtained is a green powder which dissolves in water with a blue-green coloration and in concentrated sulphuric acid with a brown coloration.

In chrome printing on cotton, yellow green tints having good properties of fastness are obtained.

Example 32 47.9 parts of chromium phthalocyaninelz4:4":4"-

tetrasulphochloride, obtained by the action of chlorosulphonic acid on chromium phthalocyanine-4z4:4:4"- tetrasulphonic acid, are discharged on to ice, and the separated reaction productis mixed as a moist paste with 250 parts of ice. The whole is rapidly added to a solution of 30.9 parts A mol) of the dipotassium salt of 6-bromo-1:3-dihydroxybenzene-4-carboxylic acid and 41.3 parts of mol) of the dipotassium salt of 3-amino- 4' hydroxy 1:1 azobenzcne 5' carboxylic acid- 6-sulphonic acid in 400 parts of water, to which have been added 10 parts of calcium carbonate. After stirring the mixture for 10 hours at 10 C., the temperature is slowly raised to 2530 C., and stirring is continued for a fur- The dyestufi is septher 30 hours at that temperature. arated in the form of its potassium salt in the manner described in Example 12.

The dyestuft so obtained is ablue-green powder which dissolves in water with a green coloration and in concentrated sulphuric acid with an olive coloration.

In chrome printing on cotton the dyestufi yields grass green tints having very good properties of fas'tness.

Example 33 96.2 parts A mol) of iron phthalocyanine tetrasulphoc'hloride, obtained by the action of chlorosulphonic acid on iron phthal ocyanine, are stirred in 300 parts of ice to form a homogeneous paste, and the latter is napidly added in an atmosphere of nitrogen while stirring, to "a solution containing 23.6 parts A mol) of the trisodium salt of 1:2:3-trihydroxy benzene-4-canboxylic acid and 75.4 parts A moi) of the dipotassium sal -t of'4-ramino- 4"hydnoxy-1:l-azlolbenzene-2:5'-dicarboxylic acid in 600 parts of waterto which have been added parts of calcium cambonate. The whole is stirred for 10 hours at 5-10 C- and for afurther hours at room temperature. The react-ion mixture is rendered acid to Congo with dilute hydrochloric acid and the precipitated dyestuif acid is separated ofi, dissolved in water and potassium carbonate, and the dyestufi is isolated with potassium chloride.

The idyestuif so obtained is a grey olive powder which dissolves in water with an olive coloration and in concentrated sulphuric acid with a brown coloration.

In chrome printing on cotton the dyestutr yields yellow olive tints.

Example 3 4 48. 1 parts mol) of iron phthalocyanine-4:4':4": 4"-tetrasu'lpl1ochloride, obtained by the action of chloroadded 15 parts of calcium carbonate. stirred at room temperature fior 24 hours and the dye- 18 sulphonic acid on the barium salt of iron phthalocy a'nine- 4:4:4:4"-tetrasulphonic acid, are mixed well with 25 0 parts of ice, and the whole is rapidly added, while stirring, to a solution of 19.8 parts A mol) of the disodium salt of 1:3-dihydroxybenzene-4-carboxylic acid and 30.9

parts A mol)-of the sodium salt of 4-amino-3-methoxy- 4-hydroxy-1 :l'-azobenzene 5 carboxylic acid in 500 parts 'of water, to which have been added 10 parts of calcium carbonate. The whole is stirred for 24 hours at room temperature and the ldyestufl? is isolated in the form of its sodium salt.

'I he dyestulf so obtained is a grey-green powder-which dissolves'in water with a green coloration and in concentrat-ed sulphuric acid with a pink coloration. In chrome printing on cotton the dyestutf yield-s dul green tints having good properties of fastness.

Example 35 93.3 parts 910 mol) of aluminium phthalocyanine tetrasulp'hochloride, obtained 'by the action of chlorosulphonic acid on aluminium phthalocyanine, are discharged on to ice and the separated reaction product is mixed as a moist paste with 300 parts of ice, and the paste is rapidly added to a solution of 39.6 parts mol) of the disodium salt of 1:3-dihydroxybenzene-4-catuboxylic acid and 30.9 parts A mol) of the sodium salt of 4-amino- 3 'methoxy 4' hydroxy 1:1' azobenzene 5' carb-oxylic acid in 600 parts of water, to which have been The Whole is st-ufi" is isolated in the form of its sodium salt.

The dyestuif so obtained is a green powder which dissolves tin water with a green coloration and in concentrated sulphuric acid with a brown coloration.

In chrome printing on cotton it yields grass green tints having good properties of Wet iastn-ess and a moderate fastness to light.

What 1 claim is:

1. A member selected from the class consisting of water-soluble mordant :azo-phthal-ocyanine dyestuffs which correspond to the formula SOLNHUN=N COOH and the alkali metal salts thereof, wherein A represents a metal-containing phthalocy-anine molecule in which the -SO2.O, -SO2.NH- and 8031-1 groups are severally present in one of the 3- and 4-position-s, said metal being selected from the group consisting of copper, cobalt, nickel, iron, chromium and aluminum, in is a member selected from the group consisting of H, halogen and CH: bound in ortho position to the SO2.O linkage, x is a member selected from the group consisting of H, CH3, OH, N02 and SOaH, y is :a member selected from the group consisting of H, CH3, OCHs, SOsH and COOH bound in :ortho-position to the azo group, z is a member selected from the group consisting of H and OCH3 bound in ortho-tposition to the SO2.NH- linkage, a and b each represents a whole number from '1 to 3 inclusive, c is a number from 0 to 2, and the sum of a+b+c=4, and wherein the SO2.NH-- group occupies one of the positions meta and para relatively to the razo linkage.

19 2. An alkali metal salt of the dyestuffof the formula COOH wherein -A represents the molecule of copper phthalocyanine to, whichthe-SO2.O and -SO2.NH- groups are bound in the 4-positions.

3. An alkalil metal salt of. the dyestuff of the formula OH 802.0 COOH) 1 COOH . SO3E wherein A represents the molecule of copper ,phthalocyanine to which the -SOz.O-, --'SO2.NH- and -SO3H groups are boundin the 3-positions;

4. .An alkali metal salt of the dyestufii of the formula wherein A represents the molecule of copper phthalocyanine to which the -SO2.O-, --SO2.NH'- and SO3H groups are bound in the 3-zpositions.

5. An alkali metal salt of the dyestuffi of the formula OH I sow-Ocoon s I COOH wherein A represents themoleculeof lbrorniirated copper' phthalocyanine; which contains 1115 percent of bromine' calculated on copper phthal-ocyanine tehrasul= and --SO3H groups are'bound in the 4-positions;

20 6. An alkali metal salt of the dyestuff of the formula 0H 5 sotogooon --S0z.NH- -N=N OCH:

wherein A represents the molecule of cobalt p'hthalocyanine to which the SO2.O- and -SO2.NH group are bound in the 4-pos-itions.

7. A process for the manufacture of a water-soluble mordant aZo-phthalocyanine dyestufi, which comprises reacting one molecular proportion of a phthalocyanine sulphoehloride which corresponds to the formula:

--(SOaH)4-n wh-erein A represents a metal containing phthalocyanine molecule in which the -SO2CL and -SO3H groups are severally present inone of the 3- 'and 4-positions, said metal being selected from the group consisting of 0019* per, cobalt, nickel, iron, chromium and aluminum, and

n represents 18. whole number from 1 to 4, with at least one molecular proportion of an :aminoazo dyestufi whicli corresponds to the formula ==N NH:

HOOD

wherein x is amemb'er selected from the group consisting of H, CH3, OH, N02 and SOsH', y is a member selected from the group consisting of H, CH3, OCHs;

SOkH and COOH bound in ortho-position to the am group, z is a member selected from the group consisting ofH and OCHa' bound in ortho posit ion to the NH2 group, and wherein the NI-1'2 group occupies one of the positions meta and pana relatively to the azo linkage; and with at least one molecular proportion of a dihydroxybenzenewarb'oxylic acid which corresponds to the formula wherein m is a member selected fir'om the group consistingofI-L halogen and CH3 bound'in'orfiho-position to :the reactingOH' group, in'an aqueous medium and in the presence ofi'an acidbinding' agent.

' References Cited in the file of this patent" UNITED STATES PZYI EN'I S 2288;478 Nadler'etal; -June 30, 1942'. 2,351,118 Haddock June '13, 1944' 2,363,906 Rossanderet al Nov. 2%,1944' 2,479,491 Haddock et-al Aug. 16,1949 

1. A MEMBER SELECTED FROM THE CLASS CONSISTING OF WATER-SOLUBLE MORDANT AZO-PHTHALOCYANINE DYESTUFFS WHICH CORRESPOND TO THE FORMULA 